CN104497471A - Method for subcritical water extrusion preparation of wood-plastic composite material - Google Patents
Method for subcritical water extrusion preparation of wood-plastic composite material Download PDFInfo
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- CN104497471A CN104497471A CN201410697662.9A CN201410697662A CN104497471A CN 104497471 A CN104497471 A CN 104497471A CN 201410697662 A CN201410697662 A CN 201410697662A CN 104497471 A CN104497471 A CN 104497471A
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a method for subcritical water extrusion preparation of a wood-plastic composite material, and belongs to the high molecular material reactive extrusion research field. A thermoplastic high molecular material accounting for 40%-80% of the total mass of reactants, wood flour accounting for 60%-15% of the total mass of the reactants, and an interfacial reactive auxiliary agent accounting for 0%-10% of the total mass of the reactants are mixed, the mixture is subjected to a melt extrusion co-blending reaction in a double-screw extruder having a subcritical water extrusion reaction condition and a certain speed, the extrusion product is subjected to cooling, granulation and drying and then is subjected to open milling by an open mill and is subjected to tabletting, and thus the wood plastic composite material is prepared. The method is further improved based on a conventional double-screw extrusion co-blending method for preparation of a wood plastic composite material. The method further enhances a reaction between plastics and wood fiber surfaces, has the co-blending and reaction processes easy to control, and is high in yield, low in energy consumption, little in pollution, and easy to scale; and the prepared wood plastic composite material has excellent mechanical properties.
Description
Technical field
The invention belongs to macromolecular material Reaction extrusion research field, relate to a kind of subcritical water and extrude the method preparing wood plastic composite; Be prepare at original twin-screw extrusion blending method the further improvement that wood plastic composite basis is carried out, namely in the twin screw extruder with subcritical water extrusion reaction condition and certain screw speed, carry out melt blending extrusion reaction.
Technical background
Timber is unique reproducible material in four large starting material (timber, cement, iron and steel, plastics) in the world, is again Ecosystem environmental protection material simultaneously.Society gets more and more for the demand of Wood products, but timber resources is mainly derived from the forest reserves, along with the development of modern social economy, society also more and more payes attention to the ecological functions of the forest reserves, which results in the anxiety of timber resources, so the rate of utilization of raising timber and reuse ratio just seem very important.
Along with going from bad to worse and a large amount of consumption of petroleum resources of environment, renewable resources vegetable fibre is receiving increasing concern in the research of life and application in producing, Biological resources not only can be made rationally to be applied the weighting agent that degradable plant fiber is used as matrix material, also can make the usage quantity of the non-renewable petroleum resources of minimizing.Wood plastic composite does not a kind ofly use any toxic chemical substance and matrix material that is durable in use, environmental protection, has water-fast, corrosion-resistant, mechanical property and the feature such as dimensional stability is good.
But wood plastic composite also also exists some technical difficult problems in the process of preparation, because wood fibre presents stronger polarity, and polymkeric substance presents nonpolar, difference between both polarity makes the consistency between bi-material poor, material occurs generally to appear in interface when destroying, and therefore the improvement of interface compatibility and interface adhesion is the key improving wood plastic composite mechanical property.
The microtexture of woody plant cells comprises fiber, conduit, parenchyma cell etc.Its structure is the key of research wood plant fibre.Microfibre is the most basic unit forming cellulose cell wall skeleton, and hemicellulose, lignin are then " weighting agents " and " tackiness agent " between microfibre (and fiber).Will partly or entirely be dissolved carrying out these " weighting agents " and " tackiness agent " in pretreated process to vegetable fibre, will be loose between microfibre, the microfibre in vegetable cell is come out.It is more thorough that these " weighting agents " and " tackiness agent " dissolve, and it is more clear that its microfibre exposes.
In the recombination process of wood plastic composite, because most of thermoplastics is nonpolar, there is hydrophobic group, and xylon surface also exists the functional groups such as a large amount of polar hydroxyl groups and phenolic hydroxyl group, these groups have very strong wetting ability, so, be difficult to the fusion realized between interface between timber and plastics.Moreover, owing to being easy to form hydrogen bond between hydroxyl, make that there is between xylon very strong Hyarogen-bonding, cause the dispersion of xylon in thermoplastics uneven.
Wood plastic composite is the thermoplastic composite that xylon disperses as disperse phase using thermoplastics as external phase, interface between two-phase becomes an entirety often through the methods combining of physics or chemistry, makes it simultaneously with the characteristic of timber and plastics.The physical modification method strengthening wood plastic composite interface binding power mainly contains: the method such as heat treating process, radiotreatment method, surface-discharge process, steam gas explosion method.Although physical treatment method is simple and practical, effect is but not necessarily obvious.Chemical process is then reduced the hydroxy number of wood surface by chemical reaction, and repelling each other between reduction polymkeric substance and wood surface acts on, and improves the bounding force at interface, or can set up the combination of physics or chemical bond between xylon and polymkeric substance.Main method has: compatilizer method, modification by coupling, surface grafting method, etherificate, acetylize etc.Wherein modification by coupling is a kind of relatively effective method.
Heat treating process is the modal treatment process of process wood fibre.For modification and the pre-treatment of wood plant fibre, containing Bound moisture and free-water in wood fibre, this is unfavorable to recombination process, the dehydration due to the rising of temperature in Blending Processes, thus produces space and inner defect in the composite.The content of the hydroxyl on xylon surface can be made by thermal treatment to decrease, be conducive to the bonding of xylon and polymeric matrix.But cell wall structure also can be made unstable, and high temperature can make vegetable fibre generation anisotropic shrinkage, breaking even to cause the destruction of cell walls.So the heat treated temperature adopted for different types of xylon is not identical yet.
Radiotreatment method a kind ofly makes material that the technology of favourable change structurally occur by outside energy.Adopt gamma radiation source to carry out radiation, need before process to add some additives, better treatment effect can be obtained like this.
Discharge process method comprises cold plasma discharge, corona discharge, sputtering discharge etc.Cold plasma discharge process mainly causes free radical and produces the effects such as polymerization, chemically modified.Sputtering discharge process mainly causes the change of timberphysics aspect, such as the roughness increase etc. on surface, to strengthen the adhesive property between interface.The effect of Corona discharge Treatment mainly improves the surface energy of macromolecular material, improves the affinity with fiber molecule surface.
Alkaline purification is a kind for the treatment of process of traditional chemical modification xylon, is widely used in very much the surface treatment of natural fiber, generally uses the sodium hydroxide solution of low concentration.Alkaline purification can dissolve the pectin of fiber surface, half fiber, xylogen and some other low molecule impurity, but can not change cellulosic chemical structure, and fiber surface can be made coarse, to enhance between plastic substrate surface in contact effectively.But alkali pretreatment requires that appointed condition is comparatively harsh, such as needs stainless steel, corrosion resistant equipment, need to consume a large amount of alkali simultaneously, running cost is increased greatly.
The acid commonly used in acid treatment has: sulfuric acid, acetic acid, hydrochloric acid etc.Concentrated acid can make Mierocrystalline cellulose effectively be degraded, but acid has corrodibility and toxicity, needs special conversion unit, and needs to design good recovery process.Although dilute acid pretreatment has solved some drawbacks of strong acid treatment, its acid-treated subsequent technique not only time-consuming but also energy consumption is large, and low in economic efficiency, environmental pollution is serious.
Surface grafting method alkene class organic monomer is grafted to xylon surface to increase a kind of close-burning method between xylon and polymkeric substance.The polymkeric substance of some vinyl monomer on wood cellulose surface grafting, can improve the water-absorbent of timber and wetting property, the binding property with plastic material thereof well.
Steam gas explosion method is a kind of physical modification method of more novel wood fibre, and its treating processes, not containing the problem of recycling the waste, has the advantages such as high-level efficiency, high strength, less energy-consumption, low stain, low cost.The part xylan in fiber can be destroyed again simultaneously, degraded product is formed to the halfway xylogen of separation.It makes the cell walls of xylplant break by causing the change of wood fibre microtexture, can remove the hemicellulose in vegetable fibre, thus make that the microfibre content in vegetable fibre increases, specific surface area increases.Meanwhile, gas explosion method can remove water-soluble substances in vegetable fibre and resinous matter, thus changes microtexture and the chemical reactivity of fiber.
Gas explosion method is generally under the pressure of 0.69 ~ 4.83MPa; with steam, fiber is heated to 160 ~ 260 DEG C; then normal pressure is decompressed to suddenly in several minutes even several seconds; instant water in cell is vaporized, the gas undergoes rapid expansion in space, create " explosion " effect; part lignin is separated; destroy xylogen and hemicellulose to cellulosic provide protection, cellulosic molecule is come out, is conducive to the interaction of xylon and thermoplastics.
Super/subcritical fluids has unique physical and chemical performance, as the dissolving power of excellence, higher ionic concn, lower viscosity, higher spread coefficient and Heat transfer coefficient.Super/subcritical fluids mainly comprises: the compound (methyl alcohol, ethanol, propyl alcohol) of water, alcohols, CO
2deng, these materials super/subcritical state has been used for biomass liquefying, process organic waste water, solid refuse, waste old etc. by report, has been widely used.
Cansell F etc. are by the research to supercritical water, concrete description has been carried out to the performance of the water of critical zone, think that water is a kind of at ceitical region physics, a kind of fluid that chemical property is adjustable, there are huge potentiality, and be a kind of eco-friendly reaction medium.The density of supercritical water sharply can increase along with the rising of pressure, can improve the solvating ability of water, can strengthen the solvability to biomass material.MasaruWatanabe etc. summarize the response characteristic of organism in super/subcritical water, also can there is continuous print change along with the change of the ambient conditions such as temperature, pressure in the character such as ionic product, specific inductivity of water, so, super/subcritical water is not only good reaction medium and solvent, or soda acid co-catalyst.Hydrolysis reaction in various degree can be there is in Mierocrystalline cellulose, hemicellulose and xylogen etc. under the condition of super/subcritical water.
Summary of the invention
The object of the invention is to provide a kind of subcritical water to extrude the method preparing wood plastic composite to improve the deficiencies in the prior art.
Technical scheme of the present invention is: prepare on the basis of wood plastic composite method at original twin screw extruder melt blending, by the wood and plastic composite preparation method for material that has now and subcritical water swelling, the method of gas explosion process wood powder combines, propose at subcritical water as under solvent and reaction-ability medium existence condition, blending reaction is melt extruded to wood powder and thermoplastics, the lignin on wood powder surface and half fibrous matter can be partly dissolved or liquefy, and to microfibre wherein formed swelling be separated, thus improve the surface reaction of microfibre in thermoplastics and wood powder, improve interface binding power, improve the mechanical property of wood plastic composite.
Concrete technical scheme of the present invention is: a kind of subcritical water extrudes the method preparing wood plastic composite, and its concrete steps are:
A. by account for reactant total mass percentage composition be 40% ~ 80% thermoplastic macromolecule material, account for reaction-ure mixture percentage composition be 15% ~ 60% wood powder and account for reaction-ure mixture be 0% ~ 10% surface reaction Reagent evaluation mixing;
B. said mixture is joined in the lump in the twin screw extruder of certain rotating speed and melt extrude, in the middle part of the machine barrel of twin screw extruder, inject water simultaneously, make it melt extrude Blending Processes and be under the state of subcritical water;
C. reaction product deviates from volatile matter through vacuum, cooling, granulation, drying, then drives refining, compressing tablet through mill, obtained wood plastic composite.
Preferably described thermoplastic macromolecule material is at least one in ABS (acrylonitrile-butadiene-styrene copolymer), PS, AS, PE or PP.
Preferably above-mentioned wood powder is the one in Eucalyptus wood powder or poplar wood powder, also can with bamboo powder etc.; The size of wood powder is generally between 40 orders to 120 orders.
Preferably above-mentioned surface reaction reagent is: any one in silane coupling agent, maleic anhydride, stearic acid, maleic anhydride grafted ABS, maleic anhydride graft PS, maleic anhydride graft AS or maleic anhydride graft PP, maleic anhydride graft PE.
The temperature of reaction that melt extrudes in preferably above-mentioned step B is 150 ~ 260 DEG C; The screw speed of preferably described certain parallel dual-screw extruding machine is 50 ~ 200r/min.
The condition melt extruding Blending Processes Subcritical water in preferred above-mentioned steps B is: temperature 150 ~ 260 DEG C; Pressure 0.4MPa ~ the 3.7MPa of general subcritical water.
Melt extrude reaction and prepare the technical process of wood plastic composite and extruder screw rod structure figure see Fig. 1 and Fig. 2.This tests screw extrusion press used is the co-rotating twin screw extruder group of second order to quadravalence, mixed by conveying screwing element, kneading screwing element, compression screwing element and left-hand thread element and form, when subcritical water extrusion reaction operates, B inlet is connected with microprocessor pump drive and tensimeter.Forcing machine temperature of reaction controls at 150 ~ 260 DEG C, and extruder screw rotating speed controls at 50rpm ~ 200rpm; The mixture of wood powder and thermoplastics is added by C charging opening, and inject water in the metering of B inlet, the speed that inlet pressure is injected by water and temperature of reaction control simultaneously; Then reaction product is begun to pratise through mill through cooling, granulation, is cooled, compressing tablet, obtained wood plastic composite.
Beneficial effect:
1. prepare compared with wood plastic composite with adopting merely twin screw extruder, because subcritical water is as the existence of solvent and reaction medium, reduce the viscosity of reaction system, enhance the dissolving of hemicellulose and xylogen in water ion and wood powder, reaction, promote its microfibre swelling and react with surface reaction reagent or plastics external phase, enhance the interface binding power of wood plastic composite, improve the material mechanical performance of wood plastic composite.
2. compared with steam gas explosion method, owing to being carry out in the twin screw extruder of continous way, will extrude blended with enhancement surface reaction become one, technological process serialization, productive rate are high, energy consumption is low, be easy to maximize, mass-producing.
3. extrude blended, surface reaction degree and sub-critical water extraction can control according to screw speed, screw slenderness ratio, screw-rod structure array configuration and temperature of reaction, processing condition are easy to optimize, and can obtain the wood plastic composite of higher force performance.
4., compared with method of chemical treatment, the inventive method aftertreatment technology is simple, and operator's labour intensity is little, contact stain is few, environmental pollution is low.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is the Assembled Twin Screw Extruder Screw figure of major equipment of the present invention :-20mm; Wherein A is gas discharge outlet, and B is water inlet, and C is charging opening;
Fig. 3 is the impact of blending temperature on ABS/ wood flour composite material tensile strength;
Fig. 4 is the impact of blending temperature on ABS/ wood flour composite material flexural strength;
Fig. 5 is the impact of blending temperature on ABS/ wood flour composite material notched Izod impact strength;
Fig. 6 is the impact of blending temperature on ABS/ wood flour composite material unnotched impact strength;
Fig. 7 is the infrared spectrogram of ABS/ wood flour composite material acetone extraction thing: 1-pure wood powder; 2-embodiment 1, blend 180 DEG C of subcritical waters are extruded; 3-embodiment 1, blend 200 DEG C of subcritical waters are extruded; 4-embodiment 2, blend 200 DEG C of subcritical waters are extruded (containing MABS);
Fig. 8 is ABS/ wood plastic composite sample section SEM photo: a-comparative example 1; B-embodiment 1; C-comparative example 2; D-comparative example 6; E-embodiment 2; F-embodiment 2 blend 200 DEG C is extruded.
Embodiment
Below by embodiment, the present invention being specifically described, it is important to point out that embodiment is only for being further detailed the present invention, can not be interpreted as limiting the scope of the invention.The person skilled in the art of this area can carry out some nonessential improvement and adjustment according to foregoing invention content.
Embodiment 1 (subcritical water is extruded): 80 order Eucalyptus wood powders, is produced by Shanghai Jia Feng wood powder company limited, above-mentioned wood powder 200g and ABS (Zhenjiang Qi Mei Chemical Co., Ltd.) 300g phase is mixed; It is 20mm length-to-diameter ratio is in the co-rotating twin screw extruder (times Long-Ke Ya mechanical means company limited of Nanjing section) of 32 that mixture adds diameter in the lump, control screw speed at 100r/min, extrusion temperature is 180 DEG C, carries out melt extruding blending reaction; At screw-rod structure figure B place, water is injected in metering simultaneously, and the pressure in forcing machine is controlled by volume pump and temperature of reaction, is 1.00MPa when 180 DEG C; Open water ring vacuum pumps while extrusion reaction, the volatile gases produced during vacuum removal reaction; Extrude product through air cooling, granulation, i.e. obtained ABS base wood-plastic composite material.
The above-mentioned product extruding blended granulation is put into mill 180 DEG C mixing, slice after mixing about 5min.After the sheet material of gained places 24 hours, with the vulcanizing press compressing tablet of 180 DEG C, the time is 300 seconds, and then chilling press is colded pressing sizing, obtains ABS base wood-plastic composite material, places the test carrying out mechanical property after 24 hours.
Embodiment 2 (subcritical water is extruded): by above-mentioned wood powder 200g, ABS (Zhenjiang Qi Mei Chemical Co., Ltd.) 275g and maleic anhydride grafted ABS (MABS, Nanjing is tough plastic cement company limited) 25g phase mixes, added in the lump by mixture in above-mentioned twin screw extruder, its screw speed, temperature, waterflood injection rate and pressure condition are identical with embodiment 1.
Embodiment 3 (subcritical water is extruded): by above-mentioned wood powder 150g, ABS (Zhenjiang Qi Mei Chemical Co., Ltd.) 325g and maleic anhydride grafted ABS (MABS, Nanjing is tough plastic cement company limited) 25g phase mixes, added in the lump by mixture in above-mentioned twin screw extruder, its screw speed, temperature, waterflood injection rate and pressure condition are identical with embodiment 1.
Embodiment 4 (subcritical water is extruded): by above-mentioned wood powder 250g, ABS (Zhenjiang Qi Mei Chemical Co., Ltd.) 225g and maleic anhydride grafted ABS (MABS, Nanjing is tough plastic cement company limited) 25g phase mixes, added in the lump by mixture in above-mentioned twin screw extruder, its screw speed, temperature, waterflood injection rate and pressure condition are identical with embodiment 1.
Comparative example 1 (dry state is extruded): not water filling in extrusion, other are identical with embodiment 1.
Comparative example 2 (dry state is extruded): not water filling in extrusion, other are identical with embodiment 2.
Comparative example 3 (dry state is extruded): add 25g maleic anhydride in reaction mixture, not water filling in extrusion, other are identical with embodiment 1.
Comparative example 4 (dry state is extruded): add 25g maleic anhydride in reaction mixture, not water filling in extrusion, other are identical with embodiment 2.
Comparative example 5 (hygrometric state is extruded): add 15g water in reaction mixture, not water filling in extrusion, other are identical with embodiment 1.
Comparative example 6 (hygrometric state is extruded): add 15g water in reaction mixture, not water filling in extrusion, other are identical with embodiment 2.
Embodiment 5 (subcritical water is extruded): 40 order poplar wood powders, produced by Shanghai Jia Feng wood powder company limited, above-mentioned wood powder 200g, HDPE (Iranian petrochemical industry company limited) 300g phase is mixed, mixture being added in the lump temperature is in the twin screw extruder of 160 DEG C, and its screw speed, waterflood injection rate and pressure condition are identical with embodiment 1.
Embodiment 6 (subcritical water is extruded): by above-mentioned wood powder 200g, HDPE (Iranian petrochemical industry company limited) 275g and maleic anhydride graft PP (MAPP, Nanjing is tough plastic cement company limited) 25g phase mixes, mixture being added in the lump temperature is in the twin screw extruder of 160 DEG C, and its screw speed, waterflood injection rate and pressure condition are identical with embodiment 1.
Comparative example 7 (dry state is extruded): do not add any auxiliary agent in reaction mixture, the twin screw extruder of 160 DEG C is extruded, not water filling in process, other conditions are identical with embodiment 1.
Comparative example 8 (dry state is extruded): add 5%MAPP in reaction mixture, the twin screw extruder of 160 DEG C is extruded, not water filling in process, other conditions are identical with embodiment 1.
The experimental formula of embodiment 1 to embodiment 6 and comparative example 1 to comparative example 8 and mechanical property result see the following form 1 and table 2 respectively.
Show in table 1 data, under dry state extrudes blending condition, relatively, after adding MABS in comparative example 2 component, the tensile strength of material and unnotched impact strength are the highest to comparative example 1,2,3,4.This illustrates that MABS has given play to the effect of obvious interfacial compatibilizer in the interface of matrix material, therefore causes the obvious increase of material mechanical performance.All containing maleic anhydride (MAH) monomer in the material component of comparative example 3,4, although the mechanical property of material comparatively comparative example 1 is significantly improved, but MAH has not given play to obvious positive effect in comparative example 4, this phenomenon and in blended material component free MAH monomer have impact on MABS and wood powder fiber in conjunction with relevant, therefore comparative example 4 is not best formula forms.
Under hygrometric state extrusion condition, relatively, the mechanical property of material is all significantly improved, and wherein particularly the raising of tensile strength and unnotched impact strength is the most obvious for comparative example 5,6 and comparative example 1,2.Under this illustrates hygrometric state extrusion condition, the swelling effect of a small amount of water may facilitate interface xylon and ABS or the reaction with MABS, causes the increase of interface bond strength, therefore causes the obvious increase of composite materials property.
Under the extrusion condition of subcritical water, embodiment 1,2 and comparative example 5,6 are relatively, the tensile strength of material and flexural strength obtain again obvious raising, this illustrates under the extrusion condition of subcritical water, owing to there being the abundant contact of high pressure water, cause interface xylon abundant swelling and with ABS or the abundant reaction with MABS, add the interface bond strength that improve wood plastic composite further, therefore cause the further increase of matrix material tensile strength and flexural strength.But due to the further reinforcement of interface binding power, reduce the surge capability of material to surging force, therefore the jagged and unnotched impact strength of embodiment 1,2 material is counter has occurred a small amount of decline.
Table 1 material prescription and ABS/ wood flour composite material mechanical property
Table 2 material prescription and HDPE/ wood flour composite material mechanical property
Show in table 2 data, under dry state extrudes blending condition, comparative example 7,8 is compared, and the stretching of comparative example 8 and flexural strength all obtain obvious raising, this illustrate MAPP can significantly improve wood mould between consistency, improve mechanical strength.
Under the extrusion condition of subcritical water, embodiment 5 is compared with comparative example 7, and tensile strength and the shock strength of material all increase, and illustrates that subcritical water has certain effect to raising interface compatibility.Embodiment 6 is compared with comparative example 8, and tensile strength, the flexural strength of material all improve, and illustrates that subcritical water and MAPP have synergy, can improve the mechanical strength of wood plastic composite on original basis further.
What change comparative example 1, embodiment 1 and embodiment 2 extrudes blending temperature, other conditions are then identical with the situation of embodiment 2 with comparative example 1, embodiment 1 respectively, and the composite materials property obtained is respectively see the curve 1 in Fig. 3, Fig. 4, Fig. 5 and Fig. 6, curve 2 and curve 3.
Curve 1,2,3 in Fig. 3,4,5,6 shows, under identical extruder screw speed conditions, with the increase of extruding blending temperature, the tensile strength of ABS/ wood flour composite material, flexural strength, notched Izod impact strength and unnotched impact strength all obviously increase, wherein curve 1 (dry state is extruded) reaches maximum value when 180 DEG C or 190 DEG C, curve 2 (subcritical water is extruded), curve 3 (subcritical water is extruded and contained MABS) then reach maximum value near 200 DEG C, after this then occur declining.This change explanation, with the increase of extruding blending temperature, subcritical water strengthens the swelling action of xylon, and the melt viscosity of ABS declines, which results in fully contacting and reinforcement that interface cohesion reacts of ABS and xylon in wood powder, therefore cause the generally increase of composite materials property.But after composite materials property reaches maximum value, with the further increase of extruding blending temperature, declining then appears in composite materials property, this and too high extrude the pyrogenic reaction that blending temperature causes wood powder, cause wood powder coking to go bad relevant.Wherein curve 2,3 is compared with curve 1, and temperature drift during maximum value appears in curve 2,3, and this is less with the oxygen touch opportunity in blend under subcritical water extrusion condition and air, causes wood powder pyrogenic reaction to die down relevant.
Curve 1,2,3 in Fig. 3,4,5,6 relatively also shows, identical extrude blending temperature condition under, under subcritical water extrusion condition (curve 2), the mechanical property of products therefrom obviously will be better than dry state extrusion condition (curve 1); Time in intermingling material containing MABS component, under its subcritical water extrusion condition (curve 3), the mechanical property of products therefrom is optimum.This phenomenon also further illustrates, under subcritical water extrusion condition, owing to there being the abundant contact of high pressure water, cause interface xylon abundant swelling and with ABS or the abundant reaction with MABS, add further and improve interface bond strength, therefore cause the further increase of composite materials property.
Curve 3 in Fig. 3,4,5,6 also shows, and under the subcritical water extrusion condition of 200 DEG C, the tensile strength of ABS/ wood flour composite material, flexural strength, notched Izod impact strength and unnotched impact strength reach 45.3MPa, 72.4MPa, 1.5kJ/m respectively
2, 6.5kJ/m
2.
The infrared spectrogram of ABS/ wood flour composite material acetone extraction thing as shown in Figure 7, wherein: 1-pure wood powder; 2-embodiment 1, blend 180 DEG C of subcritical waters are extruded; 3-embodiment 1, blend 200 DEG C of subcritical waters are extruded; 4-embodiment 2, blend 200 DEG C of subcritical waters are extruded (containing MABS); In the infrared spectra of ABS/ wood flour composite material acetone extraction thing, characteristic peak/reference peak area ratio is as shown in table 3:
Characteristic peak/reference peak area ratio in the infrared spectra of table 3 ABS/ wood flour composite material acetone extraction thing
Data presentation in curve associative list 3 in Fig. 7, with affiliated wood powder at 1240cm
-1(C-O-C) absorption peak at place is under the condition at reference peak, and the acetone extraction thing of ABS/ wood flour composite material is at 1384cm
-1(>C=CH-), 1506cm
-1(phenyl ring skeletal vibration peak) and 1640cm
-1(>C=CH
2) the charateristic avsorption band intensity at place extrudes the increase of blending temperature or adding and obviously increase with MABS composition in blend, this illustrates under subcritical water extrusion condition, with the increase of extrusion temperature, or adding with MABS in blend, cause the reinforcement of reaction between ABS and wood powder interface and interface binding power, therefore the styrene-butadiene rubber(SBR) composition caused in affiliated ABS is bonded to wood powder fiber surface and can not be fallen by extracting.
ABS/ wood plastic composite sample section SEM photo as shown in Figure 8, wherein: a-comparative example 1; B-embodiment 1; C-comparative example 2; D-comparative example 6; E-embodiment 2; F-embodiment 2 blend 200 DEG C is extruded.In Fig. 8, photo a, photo c relatively show, in photo a, xylon is pulled out, leave obvious hole, and matrix is combined with xylon closely in photo c, although xylon is also pulled out, but the superficial makings of fiber is still high-visible, illustrates that interface cohesion is tight, show the impact of the compatibilization of MABS in material component.In Fig. 8, photo b, e relatively show, although under same subcritical water extrusion condition, be pulled out and the hole that formed containing obvious xylon in photo b, but the xylon in photo e is then combined with matrix closely, show equally material form in the material impact of MABS.In Fig. 8, photo d, e, f relatively show, although all contain MABS in material composition, still can see there is combination interface gaps comparatively closely under hygrometric state extrusion condition in photo d; But under subcritical water extrusion condition or under subcritical water is extruded and raised the condition of blending temperature, photo e, f show xylon and are combined closely with material matrix, and see there is more deal resin-coated on xylon.
Claims (6)
1. subcritical water extrudes the method preparing wood plastic composite, and its concrete steps are:
A. by account for reactant total mass percentage composition be 40% ~ 80% thermoplastic macromolecule material, account for reaction-ure mixture percentage composition be 15% ~ 60% wood powder and account for reaction-ure mixture be 0% ~ 10% surface reaction Reagent evaluation mixing;
B. said mixture is joined in the lump in the twin screw extruder of certain rotating speed and melt extrude, in the middle part of the machine barrel of twin screw extruder, inject water simultaneously, make it melt extrude Blending Processes and be under the state of subcritical water;
C. reaction product deviates from volatile matter through vacuum, cooling, granulation, drying, then drives refining, compressing tablet through mill, obtained wood plastic composite.
2. method according to claim 1, is characterized in that described thermoplastic macromolecule material is at least one in ABS, PS, AS, PE or PP.
3. method according to claim 1, is characterized in that described wood powder is the one in Eucalyptus wood powder or poplar wood powder.
4. method according to claim 1, is characterized in that surface reaction reagent is: any one in silane coupling agent, maleic anhydride, stearic acid, maleic anhydride grafted ABS, maleic anhydride graft PS, maleic anhydride graft AS or maleic anhydride graft PP or maleic anhydride graft PE.
5. method according to claim 1, is characterized in that the temperature of reaction that melt extrudes in described step B is 150 ~ 260 DEG C; The screw speed of described certain parallel dual-screw extruding machine is 50 ~ 200r/min.
6. method according to claim 1, is characterized in that the condition melt extruding Blending Processes Subcritical water in step B is: temperature 150 ~ 260 DEG C.
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